Article
Chemistry, Organic
Guangyang Xu, Zhen Wang, Ying Shao, Jiangtao Sun
Summary: An enantioselective copper-catalyzed tandem cross-coupling/alkynylogous aldol reaction has been developed, yielding tetrasubstituted allenoates with central and axial chirality. This protocol utilizes copper(II) salts as a catalytic precursor, distinguishing it from previous methods using Cu(I) salts.
Article
Chemistry, Organic
Xiaoqin Ning, Yongke Chen, Fangdong Hu, Ying Xia
Summary: This study presents the palladium-catalyzed cross-coupling reactions of cyclobutanone-derived N-sulfonylhydrazones with aryl or benzyl halides, demonstrating that the metal carbene process and beta-hydride elimination can occur smoothly in strained ring systems to yield structurally diverse products. The preliminary success in asymmetric carbene coupling reactions in strained ring systems offers a promising route for the synthesis of enantioenriched four-membered-ring molecules.
Article
Chemistry, Physical
Stefan Weber, Luis F. Veiros, Karl Kirchner
Summary: Efficient manganese-catalyzed dimerization of terminal alkynes to produce 1,3-enynes is achieved in this study. The reaction is atom economic, utilizing an inexpensive catalyst with high efficiency and selectivity.
Article
Chemistry, Organic
Nidhi Mishra, Sumit K. Singh, Anoop S. Singh, Anand K. Agrahari, Vinod K. Tiwari
Summary: Glycosyl triazoles are efficient ligands for Cu-catalyzed Sonogashira reaction, overcoming challenges of sideways homocoupling reactions. High product yields can be achieved at 130 degrees C for various substrates, showing versatility of this catalytic system.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ruwei Shen, Kaixin Yin, Yishuai Fan
Summary: The copper-catalyzed reaction of alpha-halo-N-tosylhydrazones with H-phosphoryl compounds provides alkenylphosphoryl compounds with moderate to good yields. This reaction may proceed via a copper-promoted Bamford-Stevens-type reaction of an alpha-phosphorylated diazo intermediate. In the absence of a copper catalyst, the diazo intermediate is trapped by an excess H-phosphoryl compound to form alpha, N-bisphosphoryl hydrazone.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Christian Frabitore, Tom Livinghouse
Summary: This article presents a novel synthetic method for the production of saturated N-heterocyclic pharmacophore motifs, utilizing N,N-dimethylhydrazinoalkenes and diethylzinc followed by a Cu(I)-catalyzed cross-coupling reaction with 1-bromoalkynes to afford piperidines and pyrrolidines. The synthesis tolerates heteroatom-bearing alkynes and, unexpectedly, the use of ethyl propiolate as the trapping electrophile leads to selective N-functionalization with the formation of vinylogous urethanes. Alternative Cu(I) complexes were also evaluated as potential catalysts. This synthetic protocol can be easily scaled up for preparative purposes.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Shivashankar Kattela, Carlos Roque D. Correia, Abel Ros, Valentin Hornillos, Javier Iglesias-Sigu, Rosario Fernandez, Jose M. Lassaletta
Summary: A dynamic kinetic asymmetric Pd-catalyzed cross-coupling reaction of heterobiaryl bromides with ketone N-tosylhydrazones for the synthesis of heterobiaryl styrenes has been developed. The combination of Pd(dba)(2) as a precatalyst with a TADDOL-derived phosphoramidite ligand provides the corresponding coupling products with good yields and high enantioselectivities under mild conditions. Further reactions such as N-oxidation and N-alkylation of the products result in appealing functionalized axially chiral heterobiaryl derivatives.
Article
Chemistry, Organic
Qian Ye, Wencheng Huang, Li Wei, Mingzhong Cai
Summary: A highly efficient heterogeneous copper(I)-catalyzed cross-coupling of trialkylsilylethynes with N-tosylhydrazones has been achieved using SBA-15-immobilized L-proline-Cu(I) complex as the catalyst and (LiOBu)-Bu-t as the base. The reaction occurs in dioxane at 90-110 degrees C and leads to the formation of C(sp)-C(sp(3)) bonds with moderate to high yields. The recyclable nature of the immobilized copper(I) complex allows for up to 12 repeated uses without significant loss of activity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xia Chen, Xiao-Yu Zhou
Summary: A convenient, efficient, and inexpensive palladium-free catalytic system using (PPh3)(2)CuBH4 as catalyst has been developed to catalyze Sonogashira cross-coupling of o-iodoanilines with terminal alkynes under an air atmosphere, resulting in a range of 2-ethynylaniline derivatives with up to 99% yield. This protocol is scalable, and notable features include good functional group tolerance, air atmosphere, and excellent yields.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Jin-Chen Li, Bing-Xia Yan, Gang Wang, Zhi-Shi Ye
Summary: Here, we demonstrated an efficient cascade reaction of N-tosyl ortho-alkynylanilines and N-acyl ortho-alkynylanilines using Rh(COD)(2)BF4/( t )BuXantPhos as a catalyst. The reaction exhibited excellent chemoselectivity and regioselectivity, high atom-economy, and wide substrate scope. Mechanistic studies revealed that the success of this reaction relied on the strong capability of the rhodium catalyst to recognize the N-substituent group in the selective nucleophilic cyclization and alkyne insertion.
Article
Chemistry, Multidisciplinary
Long Zheng, Xueying Guo, Ying-Chao Li, Yichen Wu, Xiao-Song Xue, Peng Wang
Summary: In this study, the coupling of alkynes with Fischer-type copper carbene species bearing an alpha-siloxyl group is reported. The copper carbene species can be in situ generated from acylsilanes under photoirradiation and redox-neutral conditions. The side-arm modified bisoxazoline (SaBox) ligands play a crucial role in this coupling reaction, providing the corresponding alkynyl alcohol in high yields with remarkable heterocycle tolerance and broad substrate scope.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Mingyu Liu, Tianhua Tang, Omar Apolinar, Rei Matsuura, Carl A. Busacca, Bo Qu, Daniel R. Fandrick, Olga Zatolochnaya, Chris H. Senanayake, Jinhua J. Song, Keary M. Engle
Summary: This method presents a selective and catalytic approach for synthesizing 1,3-enynes without the need for prefunctionalized building blocks, allowing for highly regio- and stereoselective formation of the target products. It is versatile, scalable, and can operate effectively with as low as 0.5 mol % catalyst loading. Preliminary mechanistic experiments support a redox-neutral Pd(II) catalytic cycle.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Bin Li, Jiang-Ling Shi, Ying Xia
Summary: The construction of all-carbon quaternary centers in small-ring systems is an important yet challenging task in organic synthesis. In this study, we developed a practical method for building all-carbon quaternary centers in gem-difluorinated cyclopropanes (DFCs) by utilizing gem-difluorocyclopropyl bromides (DFCBs) as general and versatile building blocks. The reaction involves the participation of a gem-difluorocyclopropyl radical intermediate, which undergoes coupling with a wide range of nucleophiles under copper catalysis.
Article
Chemistry, Organic
Bin Li, Jiang-Ling Shi, Ying Xia
Summary: In this study, a practical method for building all-carbon quaternary centers in gem-difluorinated cyclopropanes was developed using gem-difluorocyclopropyl bromides as a general building block. The reaction involves the participation of a gem-difluorocyclopropyl radical intermediate, which can undergo coupling with a wide range of nucleophiles under copper catalysis.
Article
Chemistry, Organic
Qingmin Song, Yue Zhao, Shaopeng Liu, Yong Wu, Zhaohong Liu
Summary: A silver-mediated homocoupling of N-triftosylhydrazones for the construction of trans-stilbenes is described. The protocol is characterized by its suitability for both inter- and intramolecular reactions, operational simplicity, high efficiency with excellent stereoselectivity, broad substrate scope, and good functional group tolerance. A plausible mechanism involving nucleophilic attack of in situ generated sulfonium ylides on silver carbene was proposed based on experimental results and DFT calculations, which further indicates that pi-pi stacking interactions play a dominant role in stereoselectivity control.
Article
Chemistry, Organic
Fangdong Hu, Jie Jia, Ximing Li, Ying Xia
Summary: An efficient protocol has been developed for the asymmetric hydroarylation and hydroalkenylation of benzo[b]thiophene 1,1-dioxides using a rhodium(I) precatalyst and a chiral diene ligand, leading to the synthesis of 2,3-dihydrobenzo[b]thiophene 1,1-dioxides with good yields and high enantioselectivities. The merger of this asymmetric hydroarylation with downstream alkylations results in 2,3-dihydrobenzo[b]thiophene 1,1-dioxides containing two continuous quaternary stereocenters with high enantioselectivities in a diastereodivergent manner.
Article
Chemistry, Multidisciplinary
Zhong-Tao Jiang, Jiangkun Huang, Yaxin Zeng, Fangdong Hu, Ying Xia
Summary: A rhodium-catalyzed regioselective C-H allylation of simple arenes without directing groups is reported, using gem-difluorinated cyclopropanes as reactive allyl surrogates via C-C and C-F bond activation. The method offers good yields and high selectivity under mild conditions, enabling late-stage functionalization of complex bioactive molecules. The high turnover number of the rhodium catalyst in gram-scale experiments demonstrates the efficiency of the reaction, with preliminary success in kinetic resolution for enantio-enriched gem-difluorinated cyclopropanes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Jie Jia, Fangdong Hu, Ying Xia
Summary: Transition-metal-catalyzed nucleophilic dearomatization is a powerful method for obtaining functionalized heterocycles using carbon and heteroatom-based nucleophiles. These reactions are often carried out in an enantioselective manner by means of asymmetric catalysis.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Jing Zhong, Wuxin Zhou, Xufei Yan, Ying Xia, Haifeng Xiang, Xiangge Zhou
Summary: A Rh(I)-catalyzed ketone Suzuki-Miyaura coupling reaction of benzylacetone with arylboronic acid is achieved, selectively activating the C(O)-C bond on the alkyl chain containing a beta-position hydrogen. This reaction employs aminopyridine as a temporary directing group and ethyl vinyl ketone as a hydride acceptor, resulting in a series of acetophenone products with yields up to 75%.
Article
Chemistry, Multidisciplinary
Shusuke Ochi, Zining Zhang, Ying Xia, Guangbin Dong
Summary: In this study, a unique one-carbon ring-expansion strategy was developed to synthesize multi-substituted 2-indanones from benzocyclobutenones and styrene-type olefins. The use of a cationic ligandless rhodium catalyst enabled high reactivity and selectivity towards the (4+1) product. The method exhibited broad functional group tolerance and scalability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jiangkun Huang, Rui Zhang, Xiuli Wu, Guangbin Dong, Ying Xia
Summary: In this study, a Rh-catalyzed intramolecular one-carbon homologation of unstrained aryl ketones was developed through a formal 1,1-insertion process of olefins, enabled by temporary directing group (TDG)-aided C-C activation. The reaction provides a unique approach to access various substituted 1-indanones.
Article
Chemistry, Organic
Jie Jia, Fushan Yuan, Zihao Zhang, Xuejiao Song, Fangdong Hu, Ying Xia
Summary: In this study, a copper-catalyzed reaction of gem-fluorinated cyclobutenes with bis(pinacolato)diboron was reported, leading to the formation of B,F-bifunctional 1,3-dienes. The transformation was achieved through a sequence of reactions, allowing for the stereoselective synthesis of highly functionalized 1,3-dienes.
Article
Chemistry, Physical
Yang Long, Yanling Zheng, Ying Xia, Lang Qu, Yuhe Yang, Haifeng Xiang, Xiangge Zhou
Summary: A nickel-catalyzed synthesis of aryl nitriles via aryl exchange has been developed. The reaction utilizes cheap and easily handled 4-cyanopyridine as the cyanating source, allowing for the efficient conversion of various aromatic amides into aryl nitriles. The reaction exhibits wide substrate scope, good selectivity, and is complementary to traditional methods. Additionally, the mechanism is supported by the determination of two key nickel complexes through X-ray crystallography.
Article
Chemistry, Organic
Zhong-Tao Jiang, Zhengzhao Chen, Yaxin Zeng, Jiang-Ling Shi, Ying Xia
Summary: In this study, an effective method for the synthesis of chiral gem-difluorinated cyclopropanes containing an all-carbon quaternary stereocenter was reported using rhodium-catalyzed stereoablative kinetic resolution. The method showed high enantioselectivity and the resulting compounds demonstrated promising applications in various postfunctionalization reactions.
Article
Chemistry, Organic
Yulei Zhu, Yaxin Zeng, Zhong-Tao Jiang, Ying Xia
Summary: Gem-difluorinated cyclopropanes, as a special class of compounds, have attracted much attention due to their unique properties. Recently, they have emerged as a novel synthons for the synthesis of monofluoroalkenes through cross-coupling reactions.
Article
Chemistry, Physical
Yaxin Zeng, Han Gao, Yulei Zhu, Zhong-Tao Jiang, Gang Lu, Ying Xia
Summary: In this study, a synthetic method is disclosed that can introduce a fluorineallyl motif into organic molecules with site-divergent capability. This is achieved by employing gem-difluorinated cyclopropanes as the fluorineallyl source via rhodium-catalyzed C-C bond activation. The method provides two regioisomeric fluorinated skipped dienes in good yields with excellent site-selectivity. The resulting products can serve as useful building blocks for accessing various fluorine-containing molecules and are isosteric to beta, gamma unsaturated amides that show promise in medicinal chemistry.
Article
Chemistry, Multidisciplinary
Jiangkun Huang, Xufei Yan, Ying Xia
Summary: This study reveals the formal Suzuki-Miyaura coupling reaction between ketones and arylboronates without the use of a directing group. A wide range of ketones can serve as electrophiles in this reaction, and the key lies in the specific reaction sequence that achieves unstrained C-C bond activation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Xiaoqin Ning, Yongke Chen, Qian Ye, Fangdong Hu, Ying Xia
Summary: A palladium-catalyzed cross-coupling reaction between cyclobutenone N-tosylhadrazones and organohalides has been developed. The reaction involves the generation of a strained allylpalladium intermediate and subsequent electrocyclic ring opening and β-hydride elimination to produce conjugated enynes and enallenes. The broad substrate scope, high yields, and tunable product diversity make this protocol potentially valuable in organic synthesis.
Article
Chemistry, Organic
Xiuli Wu, Yaxin Zeng, Zhong-Tao Jiang, Yulei Zhu, Linshen Xie, Ying Xia
Summary: This article reports a Lewis acid-catalyzed cross-coupling reaction of gem-difluorinated cyclopropanes with nucleophiles, in which the C-F bond is activated to generate a fluoroallyl cation species that is then trapped by nucleophiles to give fluoroallylic products in good yields.
Article
Chemistry, Multidisciplinary
Yaxin Zeng, Hui Yang, Jiayi Du, Qin Huang, Guoliang Huang, Ying Xia
Summary: The control of linear/branched selectivity in transition-metal catalyzed allyl-allyl cross-coupling reactions has been investigated in this study. It has been found that the terminal/internal regioselectivity can be switched by fine-tuning the rhodium catalytic system. Different types of 1,5-dienes are produced with good yields, exhibiting isomerized terminal, internal, and terminal regioselectivity.